Barium carbonate as a modifier for certain non-rigid polymethane forms

ABSTRACT

Structural discontinuities, commonly referred to as splits and voids, which are prevalent in flexible and semiflexible polyurethane foams that have been rendered flame resistant using halogen-containing polymers in combination with antimony oxide are eliminated by the use of barium carbonate.

United States Patent Larkin et al.

BARIIIM CARBONATE s A MODIFIER FOR CERTAIN NON-RIGID .RQLXMEEQNE FQAMS Inventors: William A. Larkin, Morristown;

Robert C. Ringwood, Jr., Sewaren;

Kenneth Treadwell, Rahway, all of Assignee:

Conn.

Filed: Oct. 10, 1973 Appl. No.: 405,072

U.S. Cl.. 260/2.5 BE, 260/2.5 AJ, 260/2.5 AK,

260/41 B Int. Cl... C08g 22/44, C08g 51/56, C08g 41/04 Field of Search 260/2.5 BE, 2.5 AJ, 2.5 AK

References Cited UNITED STATES PATENTS 4/197l Harrington 260/2.5 AJ 8/197I Patton 260/2.5 BE l/l972 Treadwell 260/2.5 AJ

M & T Chemicals, Inc., Greenwich,

[ Dec. 31, 1974 3,644,229 2/1972 Butler 260/2.5 BE 3,697,456 10/1972 Pitts 260/2.5 AJ 3,718,611 2/1973 Maxey 260/2.5 BE

FOREIGN PATENTS OR APPLICATIONS 44-]4587 6/1969 Japan 260/45.75 R

OTHER PUBLICATIONS Chemical Abstracts, 722223262, 1970. Lyons, The Chemistry and Uses of Fire Retardants, Wiley Interscience, N.Y., I970, pages 293-300.

Primary Examiner-Donald E. Czaja Assistant Examiner-C. Warren Ivy,

Attorney, Agent, or FirmKenneth G. Wheeless; Robert P. Auber; Robert Spector 2 Claims, N0 Drawings 1 BARIUM CARBONATE AS A MODIFIER FOR C E RTAI N NON-RIGID FOAMS BACKGROUND This invention relates to flame retardant flexible polyurethane foams. This invention further relates to improved flame retardants for said foams wherein the, active ingredients of said flame retardants are abalogen-containing polymer and antimony trioxide.

Flexible and semiflexible polyurethane fotims have found widespread utility as insulation, structural reinforcement, cushioning and encapsulating material for electrical. and electronic components. One factor which has limited the widespread acceptance of these foams in applications such as carpet backing has been their high degree of flammability when exposed to flame or high temperatures. The combination of antimony trioxide and a halogen source such as halogencontainingpolymers imparts useful levels of flame re- 20 tardancy to a variety of cellular and non-cellular synthetic organic polymers, notably polyolefins and unsatuia'ted polyester resins. U.S. Pat. No. 3,075,928 discloses using this type of flame retardant for flexible polyurethane foams. While this combination may im- 2 part acceptable levels of flame retardancy under a given set of conditions, the interior structure of the re, sultant foam often contains numerous irregularities referred to in the art as splits and voids. The reason for this undesirable phenomenon is not completely un- 3 SUMMARY OF INVENTION This invention provides an improved flame retardant flexible polyurethane foam containing antimony trioxide and a halogen-containing polymer as the flame retarding component, wherein the improvement resides in the presence of barium carbonate in an amount between 2 and 100%, based on the weight of the antimony trioxide. i

DETAILED DESCRIPTION OF THE INVENTION The formulations employed to prepare flame retardant flexible polyurethane foams in accordance with the present invention contain 100 parts by weight of polyol, 2 to 20 parts of a mixture of antimony trioxide and barium carbonate wherein the barium carbonate 6 constitutes between 2 and'50% by weight of said mixture and between 40 and 70%, based on the weight of said mixture, of a halogen-containing polymer. The halogen-containing polymers employed in combination with the antimony trioxide include those 65 wherein the major or sole repeating unit is derived from vinyl chloride, vinyl bromide, vinyl fluoride or vinylidene chlolricleflf other repeating units are present, 7

these areconventionally derived from vinyl acetate, vin yl stearate, methacrylonitrile, acrylonitrile, and loweralkyl esters of unsaturated acids such as maleic,

5 fumaric, acrylic and methacrylic acids wherein the alcohol residue of'the ester contains between I and 18 carbon atoms. Other suitable halogen-containing poly- 'o ther polyolefin, polytetraflumers.

The foregoing halogen-containing polymers should be finely divided (powder from about'0.000l to 2 mm.) and have an intrinsic viscosity of from about 0.25 to l 2.5, preferably from about 0.5 to 1.5. The halogencontaining resinous polymers are generally used in an amount of from about 2'to I parts by weight per 100 parts by weight of the polyol to obtain the desired load bearing characteristics, but in many instances there need be only about to 40 parts, preferably from about to parts by weight. The halogen-containing polymers can be made by bulk, solvent, emulsion or suspension polymerization processes. It is preferred to use halogen-containing polymersmade by the emulsion polymerization process. Of these halogen-containing resins it also is preferred to employ polyvinyl chloride, especially emulsion polymerized polyvinyl chloride (plastisol grade). 3

Polyols used in making thepolyurethane's of the'prcsent invention are primary and secondary hydroxy-' terminated polyoxyalkylene ethers having from 2 to 4 hydroxyl groups and a molecular weight of from about 1,000 to 10,000. Theyare liquids or are-capable of Examples of polyoxyalkylene polyols include linear and branched polyethers having a plurality of ether linkages and containing at least two hydroxyl groups 40 and being substantially free from functional groups other'than hydroxyl. Among the polyoxyalkylene poly- 015 which are useful inthe practice of this invention are the polyethylene glycols, the polypropylene glycols, and polybutylene ether glycols. Polymers and copolymers of polyoxyalkylene polyols are also adaptable in the process of this'invention as well as the block copolymers of ethylene oxide and propylene oxide. Among the copolymers of polyoxyalkylene polyols thatdeserve some special mention are the ethylene oxide,

propylene oxide and butylene oxide adducts of ethyl- --ene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 2-ethylhexane-diolv 0 oxide to provide primary hydroxyl groups in the polymer and having molecular weights of from about 2000 .ene oxidel These polyethers can be characterized by the general formulae:

where in Formula A the total of subscripts, x, y, and 2 represents positive integers in the range of from to 70 and the total of subscripts a and b of Formula B represent positive integers in the range of from 20 to 100. Polyethers having a branched chain network are also useful. Such branched chain polyethers are readily prepared from alkylene oxidesof the type above described and initiators having a functionality greater than two. Branched polyethers have the advantage of making possible cross linking without the interaction of urea of urethane groups with the isocyanate groups. This has the advantage of making a larger-proportion of the isocyanate used available for the evolution of carbon dioxide and the reducing of the overall amount of isocyanate that is required in the preparation of the foamed polymer. Mixtures of polyether polyols can be used.

Likewise, there can be used as polyols grafts of ethylenically' unsaturated monomers such as acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate and the like on the polyols and having the functionality and molecular weight as shown above. Such graft polyols 'and methods for making the same are shown in the U.S.

Pats. to Stamberger, Nos. 3,304,273 and 3,383,351 and in the U.S. Pat. to Von Bonin, No. 3,294,711.

When desired, cross-linking materials having from 2 triols, trimethylolphenol, tris(hydroxyphenyl)propane,

tris(hydroxyxylyl)propane, various tetrols, such as erythritol and pentaerythritol,pentols, hexols, such as dipentaerythritol and sorbitol, as well 'as'alkyl glucosides, carbohydrates polyhydroxy fatty acid esters such as castor oil and polyoxy 'alkylated derivates of polyfunctional compounds having three or more reactive hydrogen atoms, such as, for example, the reaction product of trimethylolpropane, glycerol, 1,2,6- hexanetriol, sorbitol and other polyols with ethylene oxide, propylene oxide or other alkylene epoxides or copolymers thereof, e.g., copolymers of ethylene and propylene oxides. Grafted crosslinkers can be prepared by the process of the aforementioned Stamberger and Van Bonin U.S. Patents. Mixtures of crosslinkers can .be used. All] the polymer-forming ingredients should lene-l,3-diisocy anate, butylene-2,3-diisocyanate, alkylidene diisocyanates such as ethylidene diisocyanate and butylidene diisocyanate; cycloalkylene diisocyanates such as .cyclopentylene-l ,3-diisocyanate, cyclohexylene-l,2-diisocyanate, cyclohexylene-1,3- diisocyanate, and cycloalkylidene diisocyanates such as cyclopentylidene diisocyanate and cyclohexylidene diisocyanate; aromatic diisocyanates such as mphenylene diisocyanate, p-phenylene diisocyanate, polymethylene. polyphenylisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, bitolylene diisocyanate, naphthalene-1,4-diisocyanate, and diphenylene-4,4'-diisocyanate; aliphatic-aromatic diisocyanates such as xylylene-l,4-diisocyanate, xylylene-1,3- diisocyanate, bis(4-isocyanatophenyl) methane, bis(3- methyl-4-isocyanatophenyl) methane, and r 4,4'- diphenylpropane diisocyanate, d urylene diisocyanate, 4,4',4-tris(isocyanatophenyl) methane, 3,10- diisocyanatotricyclol5.2.1.0 decane, bis-( 2- isocyanatoethyl carbonate), and naphthalene triisocyanate and the like. Mixtures ofpolyisocyanates can be used.

The amount of polyisocyanate employed ranges from about 0.70 to 1.35 total moles of NCO (in the polyisocyanates) per total mole of active hydrogen [as determined by the Zerewitinoff method, J.A.C.S vol. 49, p. 3181 (1927)] in the polyols, crosslinkers, water, halogen-containing resins (such as partially hydrolyzed vinyl chloride-vinyl acetate copolymers) and any other active hydrogen-containing material in the polyurethane foam formulation.

Water is used as a blowing agent and is employed in amounts of from about 1.5 to 5 parts by weight per parts by weight of the polyol.

The water should be substantially or essentially pure, that is, it should be free of impurities such as ions, sols, etc. of mineral, vegetable or synthetic origin and the like which would adversely affect the foaming action or the properties of the resultant polyurethane foam. Deionized, distilled or otherwise purified water should be employed.

lf lower density and softer foams are desired there additionally can be added to the polyurethane foam formulation separately or in admixture with one of the other components, i.e., polyol or polyisocyanate, etc.,

up to about 25 parts by weight of a fluorocarbon blowing agent per 100 parts by weight of the polyol. Examl-chloro-Z carbons can be used. Mixtures of the fluorocarbons can be used. Still other blowing agents can be used in full or partial replacement of the fluorocarbons such as propane, butane, pentane, pentene, hexane and so forth, and mixtures thereof, particularly where precautions are taken to prevent explosions or where removal of gasses is provided. See US Pat. Nos. 3,072,582 and 3,391,093.

Catalysts for the polyetherpolyol-polyisocyanate reaction can be any catalyst heretobefore used in the art particularly the metal-containing catalysts. Examples of such catalysts, also referred to as gel catalysts, are (l) tertiary phosphines such as trialkylphosphines,

dialkyl-benzylphosphines, and the like; (2) strong bases such as the alkali and alkaline earth metal hydroxides, alkoxides, and phenoxides; (3) acidic metal salts of strong acids such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate, bismuth chloride, and the like; (4) chelates of various metals such as those which can be obtained from acetylacetone, benzolyacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone2-carboxylate, and the like, with various metals such as Be, Mg, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, Ni, or ions such as MoO and the like; (5) alcoholates and phenolates of various metals such as Ti(OR),, Sn(OR) Sn(OR) Al(OR) and the like, wherein R is alkyl or aryl, and the reaction products of alcoholates with carboxylic acids, betadiketones and 2-(N,N-diarylamino) alkanols, such as the well known chelates of titanium obtained by said or equivalent procedures; (6) salts of organic acids with metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni, and Cu, including, for example, sodium acetate, potassium laurate, calcium hexanoate, stannous acetate, stannous octoate, stannous oleate, lead octoate, metallic driers such as manganese, cobalt, or lead naphthenate and the like; (7) organometallic derivatives of tetravalent tin, trivalent and pentavalent arsenic, antimony and bismuth, and metal carbonyls of iron and cobalt; and (8) the dialkyltin salts of carboxylic acids,,e.g., dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis( 4-methylaminobenzoate), dibutyltin-bis(6methylaminocaproate), and the like; as well as a trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, or a dialkyltin dichloride, such as trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2- methylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and the like and mixtures thereof. Preferred catalysts to use are the divalent tin salts of carboxylic acids having from 2 to 18 carbon atoms. These catalysts are used in an amount of from about 0.1 to 0.9 part by weight per 100 parts by weight of the polyetherpolyol. It is less preferable to use catalysts such as the metal salts, alcoholates, hydroxides, alkoxides and phosphines, especially in large amounts, where resins containing ester groups in a substantial amount are used since they tend to hydrolyze the ester linkages thereby causing scission of the backbone polymer chain and lowering of the physical and chemical prop erties of the resultant foams, especially under conditions of high temperature and humidity.

Surfactants or emulsifiers are necessary to provide the desired cell formation and growth. Polysiloxanepolyoxyalkylene block copolymers are preferred. Polysiloxanepolyoxyalkylene block copolymers are described in US. Pat. Nos. 2,834,748 and 2,917,480. Another useful class of emulsifiers are the nonhydrolyzable polysiloxane-polyoxyalkylene block covpolymers. This class of compounds differs from the above-mentioned polysiloxane-polyoxyalkylene block copolymers in that the polysiloxane moiety is bonded to the polyoxyalkylene moiety through direct carbonto-silicon bonds, rather than through carbon-to-oxygen-to-silicon bonds. These copolymers generally con tain from 5 to weight percent, and preferably from 5 to 50 weight percent, of of polysiloxane polymer with the remainder being polyoxyalkylene polymer. The copolymers can be prepared, for example, by heating a mixture of (a) a polysiloxane polymer containing a silicon-bonded, halogen'substituted monovalent hydrocarbon group and (b) an alkali metal salt ofa polyoxy- .alkylene polymer to a temperature sufficient to cause the polysiloxane polymer and the salt to react to form the block copolymer. Althoughthe use of an emulsifier is desirable to influence the type of foam structure that is formed, the foam products of the invention can be prepared without emulsifiers. Still other polysiloxane polyoxyalkylene copolymers known to the art may be employed as well as silicones, turkey red oiland so forth. The surfactant is used in an amount of from about-0.3 to 2.5 parts by weight per parts by weight of the polyether polyol.

It is highly advantageous to incorporate into the urethane compositions of the present invention at least one organic tertiary amine catalyst, preferably together with a metal-containing co-catalyst. The amount of organic amine catalyst may comprise, per 100 parts by weight of organic polyol, about 0.05 to 3.2 parts by weight. In the case of the polyether polyols where a metal catalyst is used for the urethane-forming reaction, it is preferred to use only from about 0.05 to 0.9 part by weight of the amine. On the other hand, where the tertiary amine is taking care of both the foaming (H O+NCO) and network (ROH+NCO) reactions, the tertiary amines should be used in an amount of from about 0.9 to 3.2 parts by weight, based on 100 parts by weight of the polypolyol.

In the urethane compositions of the invention there may be used a wide variety of organic tertiary amine catalysts. Such organic amines, include, among others, tri-ethylene diamine, triphenyl amine, triethylamine, N,N,N,N'-tetramethyl-l,3-butane diamine, N-methyl morpholine, N-ethyl morpholine, N-acetyl morpholine, N-octyl morpholine, N-coco morpholine, N-phenyl morpholine, N-hydroxyl ethyl morpholine, N-hydroxyl rneth yl morpholine, 4,4-dithiodimorpholine, dimethyl piperazine, N,N,N,N-tetramethyl propane diamine,

trimethyl aminoethyl piperazine, N,N-dimethyl ethanolamine, dimethyl hexadecylamine, l-(2-ethyl-lhexenyl) piperazine, tri-n-octylamine, trimethylamine, N,N-dimethyl benzyl amine, triethanolamine, l,2,4-trimethylpiperazine, N-methyl dicyclohexylamine, and mixtures thereof.

Other well known constituents can be added to the polyurethane foam recipe such as clay, talc, TiO silica and hydrated silica, CaCO metal chromates, barytes, phthalcoyanine green or blue pigments, red iron oxide, conventional stabilizers, carbon black, dyes, toners, epoxidized soy bean oil (Paraplex 6-62), epoxides (Epon 828), tricresyl phosphate, antioxidants, fungicides, bacteriostats and the like. These constituents can be added in various amounts to the foamingingredients to achieve the desired properties in the resultant flexible, low density foams.

The flexible, cellular urethane-vinyl chloride polymeric foams of the present invention can be used as cushions, mattresses, pillows, cushioning material for furniture and automobiles, rug underlay and especially as interior automobile door panels, head rests, and so forth. I

The polyurethane foams of the present invention can be formed. by a process known in the art as the oneshot" process or by a two-step process involving, first, the preparation of a prepolymer, the well known semiprepolymer or quasi-prepolymer technique. There all or a portion of the polyol is reacted with all of the organic polyisocyanate, providing a reaction product which contains a high percentage free isocyanate group and which is reacted with the remaining portion of the hydroxyl-terminated polyol or a cross linker, together with water, catalysts, metal oxides and the halogen-containing polymer to form a rubbery, cellular, elastic product.

Regardless of the particular technique employed to disperse the antimony trioxide, halogen-containing polymer and barium carbonate,these can be dispersed in either the polyol phase or the isocyanate phase prior to the time at which the two are combined together with the other ingredients to obtain the cellular polyurethane. Alternatively, the dispersion can be prepared in a mixture of the isocyanate and polyol. To facilitate processing and increase efficiency of the flame retardant the average particle size of the solid additives should be between 0.5 and 15 microns, the small sizes and narrower ranges of particle size distribution being preferred.

The following example illustrates a preferred embodiment and should not be interpreted as limiting the scope of the invention as defined in the appended claims. All parts are by weight unless otherwise indicated.

EXAMPLE Parts by Weight Ingredient in formulation Polyol I I00 isocyanate 52.0 52.0 Surfactant L0 1.0 Water 4.0 4.0 Polyvinyl chloride resin 22.0 22.0 Stannous octoate 0.4 0.4 Blowing catalyst 0.15 0.15 Zinc Oxide 3.0 3.0 Antimony trioxide 7.0 Antimony trioxide/barium carbonate polyoxypropylene trinl. molecular weight 3000 a mixture of m-and ptqlyl diisocyanates. exhibiting a weight ratio of 80/20. respectively a a non-hydrolyzable dimethyl siloxane alkylene oxide copolymer available as L550 from Union Carbide Chemical Corp.

a dispersion grade vinyl chloride homopolymer available as Geon 121 from the Goodrich Chemical Company a mixture of between 50 and 60; by weight of antimony tris tallate anti 40-50% by weight of the potassium salt of Nopchelate 05 as disclosed in Table of US. Patent 3,620,985. which is hereby incorporated by reference. Nopchelate OStsold by Nopco Chemical Company. Newark. New Jersey) comprises nitrogen-containing organic acids having the formula (,H ,,O,N wherein x ranges from 10 to Iii and y ranges from 2| to .17 and alkali metal stills of saitl acids. "Nopchelate OS" exhibits a molecular weight of approximate! 270. a specific gravity of L0 and contains (1.75; potassium (equivalent). approximately 21; nitrogen. solids. 201 xylene. and is a solution of alkyl amiilo miuies in xylene. A more complete description of the compound is found in 11.5 Pat. No 3,088,793: 3,088,7991't1nd 3.345.344.

The formulations were prepared by gradually adding the antimony oxide or mixture of antimony oxide and barium carbonate to the polyol with vigorous stirring to ensure formation of a uniform dispersion. The mixture of barium carbonate and antimony trioxide had been previously prepared by combining the two solids in the desired proportions to obtain a homogenous mixture.

The remaining components of the formulation, with the exception of the diisocyanate, were then added to the resultant dispersion, which was then mixed well to obtain a homogeneous composition. This composition was then combined with the diisocyanate and stirred vigorously for between 8 and 10 seconds, poured into an open top square containing measuring 12 inches (30 cm.) along each side and allowed to foam. Sections measuring 10 X l0 X l inch (25 X 25 X 2.5 cm.) were sliced from the resultant block of foam.

The foam which did not contain barium carbonate exhibited numerous large splits and voids throughout the sample to the extent that the foam was not considered to be acceptable as an article of commerce. The

sample containing barium carbonate had the desirable small uniform cell structure which characterizes a commercially useful product. i i

The flame retardancy of each foam sample was evaluated by placing it on a horizontally oriented square perforated metal platemeasuring 10 inches along each edge. A square metal frame wherein the length of each outer edge was 10 inches 25 cm.) and the length of each inner edge was 8 inches (20 cm.) was placed on the foam sample such that the outer edges of the frame coincided with the four vertical sides of the sample, leaving an area of 64 square inches (412 sq. cm.) of foam exposed. The frame measured 0.13 inch (0.33 cm.) in thickness.

A table containing methanamine was placed in the center of the exposed area of the foam sample and ignited with a match. The sample was rated selfextinguishing if the resultant flame was extinguished before it had advanced to within one inch of the inner edge of the frame at any point. Three samples were tested using each of the foregoing formulations A and ide, the combined weight of antimony trioxide and barium carbonate constituting between 2 and 20%, based on the weight of said polyol.

2. The improved flame retardant urethane foam of claim 1 wherein the halogen-containing polymer is a homopolymer or copolymer of vinyl chloride and exhibits an average particle size of between 0.0001 and 

1. IN AN IMPROVED FLAME-RETARDANT FLEXIBLE OR SEMIFLEXIBLE FOAM COMPRISING THE REACTION PRODUCTION OF A. 100 PARTS BY WEIGHT OF A POLYOL SELECTED FROM THE GROU CONSISTNG OF PRIMARY AND SECONDARY HYDROXYTERMINATED POLYALKYLENE ETHERS EXHIBITING A MOLECULAR WEIGHT BETWEEN 1,000 AND 10,000; B. AN ORGANIC-DI OR TRIISOCYANATE IN AN AMOUNT BETWEEN 0.70 AND 1.35 MOLES PER TOTAL MOLE OF ACTIVE HYDROGEN PRESENT, AS DETERMINED BY THE ZEREWITINOFF METHOD; C. BETWEEN 1.5 AND 5 PARTS OF WATER OR OTHER BLOWING AGENT; D. BETWEEN 0.1 AND 0.9 PARTS OF A GEL CATALYST; E. A FLAME RETARDANT CONSISTING ESSENTIALLY OF ANTIMONY TRIOXIDE AND BETWEEN 2 AND 100 PARTS OF A FINELY DIVIDED HALOGEN-CONTAINING POLYMER; THE IMPROVEMENT WHICH COMPRISES THE PRESENCE OF BARIUM CARBONATE IN AN AMOUNT BETWEEN 2 AND 50% BASED ON THE WEIGHT OF SAID ANTIMONY TRIOXIDE, THE COMBINED WEIGHT OF ANTIMONY TRIOXIDE AND BARIUM CARBONATE CONSTITUTING BETWEEN 2 AND 20%, BASED ON THE WEIGHT OF SAID POLYOL.
 2. The improved flame retardant urethane foam of claim 1 wherein the halogen-containing polymer is a homopolymer or copolymer of vinyl chloride and exhibits an average particle size of between 0.0001 and 2 mm. 